JP2014025066A - Composite composition of a polyimide copolymer and inorganic particles, method for manufacturing the same, molded artifact including the same, and display device having the molded artifact - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite composition of a polyimide copolymer and inorganic particles which has, apart from being excellent in terms of solvent solubility, workability, and optical characteristics and being capable of attenuating the thermal expansion coefficient, a high heat resistance and excellent mechanical strengths and which can be used favorably for manufacturing molded artifacts, above all for manufacturing films for display devices demanded to meet advanced heat resistance and transparency standards, a method for manufacturing the same, a molded artifact including the same, and a display device having the molded artifact.SOLUTION: Provided is a composite composition of a polyimide copolymer and inorganic particles including, as a copolymer comprising first repeating units or second repeating units including imide repeating units or amic acid repeating units forming imide repeating units as a result of imidation and third repeating units including amide repeating units, a copolymer in which at least one terminal thereof has been substituted with a substituted or un substituted siloxane or silanol group; and inorganic particles or precursors thereof.

Description

  The present invention relates to a composite composition of a polyimide copolymer and inorganic particles, a production method thereof, a molded article including the same, and a display device including the molded article.

  Colorless and transparent materials have been studied in various ways depending on various applications such as optical lenses, functional optical films, and disk substrates. However, as information devices are rapidly becoming smaller and lighter and display elements are becoming more precise, The functions and performance required of the device itself are gradually becoming higher and more sophisticated.

  Therefore, studies on colorless and transparent materials excellent in transparency, heat resistance, mechanical strength, and flexibility are being actively conducted (see, for example, Patent Documents 1 to 6).

JP 2005-187768 A Korean Published Patent No. 2003-0027249 Korean Published Patent No. 2005-0072182 JP-A-8-104749 JP 2010-180292 A Japanese Patent Laid-Open No. 3-207717

  An object of the present invention is to provide a composite composition of a polyimide copolymer and inorganic particles that are excellent in transparency, heat resistance, mechanical strength and flexibility.

  Another object of the present invention is to provide a composite composition of poly (amide-imide) copolymer and inorganic particles having excellent transparency, heat resistance, mechanical strength and flexibility.

  Still another object of the present invention is to provide a molded article comprising a composite composition of the polyimide copolymer and inorganic particles or a composite composition of the poly (amide-imide) copolymer and inorganic particles.

  Still another object of the present invention is to provide a display device including the molded product.

  According to one embodiment of the present invention, an imide repeating unit represented by the following general formula 3, an amic acid repeating unit that forms the imide repeating unit of the above general formula 3 by imidization, or a combination of these repeating units. A second repeating unit comprising a repeating unit of 1 and an imide repeating unit represented by the following general formula 4, an amic acid repeating unit that forms an imide repeating unit represented by the above general formula 4 by imidization, or a combination of these repeating units A copolymer comprising one or more repeating units and a repeating unit represented by the following general formula 1, a repeating unit represented by the following general formula 2, or a third repeating unit including a combination of these repeating units. And at least one end of the copolymer has a substituted or unsubstituted silo. A copolymer which is substituted by an acid or a silanol group, comprising the inorganic particles or a precursor thereof, a composite composition of copolymer and the inorganic particles is provided. The amic acid repeating unit means “a repeating unit constituting polyamic acid” which is a precursor of polyimide.

In the above general formula 3 or general formula 4,
R ¹⁰ is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C1-C30 aliphatic organic group, a substituted or unsubstituted C3-C30 alicyclic organic group, a substituted or unsubstituted A C6-C30 aromatic organic group, or a substituted or unsubstituted C2-C30 heterocyclic group,
R ¹¹ is the same or different in each repeating unit, and each independently includes a substituted or unsubstituted C6-C30 aromatic organic group, and the aromatic organic group is one aromatic ring, Two or more aromatic rings are bonded to each other to form a condensed ring, or two or more aromatic rings are a single bond, or a fluorenylene group, -O-, -S-, -C (= O)- , —CH (OH) —, —S (═O) ₂ —, —Si (CH ₃ ) ₂ —, — (CH ₂ ) _p — (where 1 ≦ p ≦ 10), — (CF ₂ ) _q -(Where 1 ≦ q ≦ 10), —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or —C (═O) NH—
R ¹² and R ¹³ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, an ether group (—OR ²⁰⁸ , where R ²⁰⁸ is a C1-C10 aliphatic organic group). , A silyl group (—SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substitution Or an unsubstituted C1-C10 aliphatic organic group, or a C6-C20 aromatic organic group,
n7 and n8 are each independently an integer of 0 to 3.

In the above general formula 1,
R ¹ is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C3-C30 alicyclic organic group, a substituted or unsubstituted C6-C30 aromatic organic group, or a substituted or non-substituted group. Containing a substituted C2-C30 heterocyclic group,
R ² is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C6-C30 aromatic organic group;
R ³ and R ⁴ are the same or different and are each independently a hydrogen element, a halogen element, a hydroxy group, or an ether group (—OR ²⁰⁰ , where R ²⁰⁰ is a C1-C10 aliphatic organic group). , A silyl group (—SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substitution Or an unsubstituted C1-C10 aliphatic organic group, or a C6-C20 aromatic organic group,
n1 and n2 are each independently an integer of 0 to 4.

In the above general formula 2,
R ⁵ is the same or different in each repeating unit, each independently a substituted or unsubstituted C6-C30 aromatic organic group,
R ⁶ and R ⁷ are the same or different and are each independently an electron withdrawing group;
R ⁸ and R ⁹ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, an ether group (—OR ²⁰⁴ , where R ²⁰⁴ is a C1-C10 aliphatic organic group), A silyl group (—SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substituted or An unsubstituted C1-C10 aliphatic organic group, or a C6-C20 aromatic organic group,
n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3 + n5 is an integer of 4 or less,
n4 is an integer of 1 to 4, n6 is an integer of 0 to 3, and n4 + n6 is an integer of 4 or less.

  The repeating unit represented by the above general formula 3 may include an imide repeating unit represented by the following general formula 5 or an amic acid repeating unit capable of forming an imide repeating unit represented by the above general formula 5 by imidization. .

In the above general formula 5,
R ¹¹ , R ¹² , R ¹³ , n7 and n8 are the same as described in the general formula 3.

Specifically, in the above general formula 1, R ¹ may be selected from the group represented by the following general formula.

Specifically, in the general formula 2, wherein ^{R 6} and ^{R 7} are the same or different and are _{independently, -CF 3, -CCl 3, -CBr} 3, -CI 3, -F, -Cl, - _{br, -I, -NO 2, -CN} , or may be a -COCH ₃ or _-CO 2 _C 2 _{H 5.}

Specifically, in the general formula 1 and the general formula 2, the R ² and R ⁵ are the same or different and can be independently selected from the group represented by the following general formula.

In the above general formula:
R ^{18 to} R ²⁹ are the same or different and are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted C1-C10 aliphatic organic group, or a substituted or unsubstituted C6-C20 aromatic. Group organic group,
n11 and n14 to n20 are each independently an integer of 0 to 4,
n12 and n13 are each independently an integer of 0 to 3.

More specifically, R ² and R ⁵ may be the same or different and may be independently selected from the group represented by the following general formula.

  On the other hand, the third repeating unit may further include a repeating unit represented by the following general formula 6.

In the above general formula 6,
R ¹⁴ is the same or different in each repeating unit, and each independently represents —O—, —S—, —C (═O) —, —CH (OH) —, —S (═O) ₂ —, —Si (CH ₃ ) ₂ —, — (CH ₂ ) _p — (where 1 ≦ p ≦ 10), — (CF ₂ ) _q — (where 1 ≦ q ≦ 10), —C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -C (= O) NH-, or a substituted or unsubstituted C6-C30 aromatic organic group, wherein the aromatic organic group is one aromatic Or two or more aromatic rings are bonded to each other to form a condensed ring, or two or more aromatic rings are a single bond or a fluorenylene group, -O-, -S-, -C (= O) -, - CH (OH) -, - S (= O) 2 -, - Si (CH 3) 2 -, - (CH 2) p - ( wherein, ≦ p ≦ 10), - ( CF 2) q - ( _{wherein, 1 ≦ q ≦ 10),} - C (CH 3) 2 -, - C (CF 3) 2 - or -C (= O) NH- Connected by a functional group of
R ¹⁵ is the same or different in each repeating unit, each independently a substituted or unsubstituted C6-C30 aromatic organic group;
R ¹⁶ and R ¹⁷ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, or an ether group (—OR ²¹² , where R ²¹² is a C1-C10 aliphatic organic group). A silyl group (—SiR ²¹³ R ²¹⁴ R ²¹⁵ , wherein R ²¹³ , R ²¹⁴ and R ²¹⁵ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substitution Or an unsubstituted C1-C10 aliphatic organic group, or a C6-C20 aromatic organic group,
n9 and n10 are each independently an integer of 0 to 4.

  The copolymer is a first repeating unit including a repeating unit represented by the above general formula 3 that is the same or different from each other, an amic acid repeating unit that forms a repeating unit of the above general formula 3 by imidization, or a combination of these repeating units. 1 to 1,000 may be included.

  The copolymer may be the same or different from each other, the second repeating unit including the repeating unit represented by the above general formula 4, the amic acid repeating unit that forms the repeating unit of the above general formula 4 by imidization, or a combination of these repeating units. 1 to 1,000 may be included.

  Each of the copolymers may have a weight average molecular weight of about 500 g / mol to about 200,000 g / mol.

  In the copolymer, the total number of moles of the first repeating unit including the repeating unit represented by the general formula 3, the amic acid repeating unit that forms the repeating unit of the general formula 3 by imidization, or a combination of these repeating units. And the total number of moles of the repeating unit represented by the general formula 4, the amic acid repeating unit that forms the repeating unit of the general formula 4 by imidization, or the second repeating unit including a combination of these repeating units, It may have a molar ratio of about 99: 1 to about 1:99.

  The copolymer has 1 to 1,000 third repeating units including the same or different repeating units represented by the above general formula 1, the repeating units represented by the above general formula 2, or a combination of these repeating units. May be included.

  The copolymer includes a repeating unit represented by the above general formula 3 or 4 or an amic acid repeating unit that forms a repeating unit of the above general formula 3 or 4 by imidization, or a combination of these repeating units. 3rd repeating unit containing the total number of moles of 1 repeating unit and 2nd repeating unit, the repeating unit represented by the said General formula 1, the repeating unit represented by the said General formula 2, or a combination of these repeating units The total number of moles of may have a molar ratio of about 95: 5 to about 5:95.

  The repeating unit represented by the general formula 1 may include a repeating unit represented by the following general formulas 7 to 9, and the repeating unit represented by the general formula 2 is a repeating unit represented by the following general formulas 10 to 12. The repeating unit represented by the general formula 3 may include a repeating unit represented by the following general formula 13, and the repeating unit represented by the general formula 4 may be represented by the following general formula 14: The repeating unit represented by the general formula 6 may include a repeating unit represented by the following general formulas 15 to 17.

  The copolymer may contain a repeating unit represented by the general formula 10, a repeating unit represented by the general formula 13 and a repeating unit represented by the general formula 14.

  In the composite composition of the copolymer and inorganic particles according to the embodiment, at least one terminal of the copolymer is substituted with a substituted or unsubstituted siloxane or silanol group.

  The substituted or unsubstituted siloxane or silanol group substituted at at least one terminal of the copolymer is a siloxane or silanol group represented by the following general formula 20:

In the general formula 20,
Ra is a substituted or unsubstituted alkyl group (alkylene group), a substituted or unsubstituted alkenyl group (alkenylene group), a substituted or unsubstituted alkynyl group (alkynylene group), a substituted or unsubstituted cycloalkyl group (cycloalkylene). Group), substituted or unsubstituted cycloalkenyl group (cycloalkenylene group), substituted or unsubstituted cycloalkynyl group (cycloalkynylene group), substituted or unsubstituted aryl group (arylene group), or substituted or unsubstituted It may be an aralkyl group (aralkylene group),
Rb to Rd are the same or different and are each independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, or a C6-C It may be a C18 aryl group.

  Specifically, the general formula 20 may be selected from the group represented by the following general formula.

  In the above general formula, Re to Rg are the same or different and are each independently a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C3 to C20 cycloalkyl group, or a C6. It may be a C18 aryl group.

  The inorganic particles or precursors thereof contained in the composite composition of the copolymer and inorganic particles are oxides or water of one or more elements selected from the group consisting of Ti, Si, Al, Zr, Sn, B, and Ce. It may be an oxide or a precursor capable of forming the oxide or hydroxide.

  Specifically, the precursor compound capable of forming an oxide or hydroxide of the Ti, Si, Al, Zr, Sn, B, or Ce element is an alkoxide, ester, acetylacetonate, or halide of the element. A halide).

Specifically, the inorganic particles may be silica (SiO ₂ ) or TiO ₂ .

  The silica precursor may contain an organic silica precursor or an inorganic silica precursor, and the organic silica precursor may be a compound represented by the following general formula.

In the above general formula:
Rh to Rm are the same or different and are each independently a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, or a C6-C18 aryl group. It may be.

  The inorganic silica precursor may contain tetraethylorthosilicate (tetraethoxysilane; TEOS).

As the TiO ₂ precursor, tetraisopropyl orthotitanate may be used.

  The inorganic particles or inorganic particle precursors may be included in a content sufficient to provide about 5 wt% to about 95 wt% inorganic particles based on the weight of the copolymer. Specifically, the inorganic particles or inorganic particle precursor is about 10 wt% to about 90 wt%, more specifically about 15 wt% based on the weight of the copolymer. % To about 80% by weight of inorganic particles may be included.

  According to another embodiment of the present invention, a molded article including a composite composition of the polyimide copolymer and inorganic particles is provided.

  Specifically, the molded article may be a film, a fiber, a coating material, or an adhesive.

  The molded article may have a total light transmittance of about 70% or more in a wavelength range of 360 nm to 700 nm, or a light transmittance of about 55% or more with respect to light having a wavelength of 430 nm.

  The molded article may have an average coefficient of thermal expansion (CTE) of about 30 ppm / ° C. or less in a temperature range of about 50 ° C. to about 400 ° C.

  The molded article may have a haze of about 7% or less.

  The molded article may have a yellowness (YI) of about 20% or less.

  The molded article may have a glass transition temperature (Tg) of about 400 ° C. or higher.

  According to still another embodiment of the present invention, a display device including the molded product is provided.

  Specific details of other embodiments of the present invention are included in the following detailed description.

  The composite composition of a copolymer and inorganic particles according to an embodiment of the present invention is excellent in solubility in a solvent, processability, and optical characteristics, and can have a low thermal expansion coefficient and high heat resistance. In addition, since it has mechanical strength, it is suitably used for the production of molded products, particularly for the production of films for display devices that require high heat resistance and transparency.

It is sectional drawing of the liquid crystal display device which concerns on one Embodiment of this invention. It is sectional drawing of the organic light emitting diode which concerns on one Embodiment of this invention. 1 schematically illustrates a reaction scheme for preparing a poly (amide-amide acid) copolymer having a silanol group substituted at one end according to an embodiment of the present invention. According to an embodiment of the present invention, after preparing a nanocomposite solution by mixing an inorganic particle precursor with a poly (amide-amide acid) copolymer having a silanol group substituted at one end, and spin-coating it, 1 schematically shows a process of producing a nanocomposite film by drying and imidization. It is a graph which measures and shows the light transmittance according to wavelength by the content of silica of the nanocomposite film manufactured according to the synthesis example 2. FIG. It is a graph which measures and shows the transmittance | permeability by a wavelength, adjusting the content of a silica to 40 weight%, 50 weight%, and 60 weight%. It is a graph which shows the light transmittance in 430 nm with respect to the content of the silica of each nanocomposite film manufactured according to the synthesis example 2. It is a graph which measures and shows the dimensional change with temperature of each nanocomposite film manufactured according to the synthesis example 2. FIG.

  Hereinafter, embodiments of the present invention will be described in detail. However, this is merely an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

In this specification, unless otherwise specified, “substituted” means that one or more hydrogen atoms in the functional group of the present invention are a halogen atom (F, Br, Cl or I), a hydroxy group, a nitro group, a cyano group. Group, amino group (NH ₂ , NH (R ¹⁰⁰ ) or N (R ¹⁰¹ ) (R ¹⁰² ), wherein R ¹⁰⁰ , R ¹⁰¹ and R ¹⁰² are the same or different and are each independently C1 to C10 Amidino group, hydrazine group, hydrazone group, carboxyl group, ester group, ketone group, substituted or unsubstituted alkyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl Groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted heteroaryl groups, and substituted or unsubstituted Means those substituted with one or more substituents selected from the group consisting of heterocyclic group, the substituent may form a ring are connected to each other.

  In this specification, unless otherwise specified, the “alkyl group” means a C1-C30 alkyl group, specifically, a C1-C15 alkyl group, and the “cycloalkyl group” means , C3-C30 cycloalkyl group, specifically, C3-C18 cycloalkyl group, "alkoxy group" means C1-C30 alkoxy group, specifically, C1 -C18 alkoxy group means "ester group" means C2-C30 ester group, specifically means C2-C18 ester group, and "ketone group" means C2-C18 ester group. Means a C30 ketone group, specifically a C2-C18 ketone group, and an “aryl group” means a C6-C30 aryl group, specifically a C6-C18 aryl group. Means the group `` Arkeni "Group" means a C2-C30 alkenyl group, specifically, a C2-C18 alkenyl group, and "Alkynyl group" means a C2-C30 alkynyl group, especially a C2-C18 alkynyl group. Group means an "alkylene group" means a C1-C30 alkylene group, specifically, a C1-C18 alkylene group, and an "arylene group" means a C6-C30 arylene group. Specifically, it means a C6-C16 arylene group.

Further, in this specification, unless otherwise specified, the “aliphatic organic group” means a C1-C30 alkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group, a C1-C30 alkylene group, C2-C30 alkenylene group or C2-C30 alkynylene group means, specifically, C1-C15 alkyl group, C2-C15 alkenyl group, C2-C15 alkynyl group, C1-C15 alkylene group. , C2-C15 alkenylene group, or C2-C15 alkynylene group, and "alicyclic organic group" means C3-C30 cycloalkyl group, C3-C30 cycloalkenyl group, C3-C30 cyclohexane. Alkynyl, C3-C30 cycloalkylene, C3-C30 cycloalkenylene, or C3-C30 cyclo A alkynylene group means a C3-C15 cycloalkyl group, a C3-C15 cycloalkenyl group, a C3-C15 cycloalkynyl group, a C3-C15 cycloalkylene group, a C3-C15 cycloalkenylene group. Or a C3-C15 cycloalkynylene group, and the “aromatic organic group” means one aromatic ring, two or more aromatic rings together forming a condensed ring, or two or more aromatic rings Is a single bond, or a fluorenylene group, —O—, —S—, —C (═O) —, —CH (OH) —, —S (═O) ₂ —, —Si (CH ₃ ) ₂ —. , — (CH ₂ ) _p — (where p is in the range 1 ≦ p ≦ 10), — (CF ₂ ) _q — (where q is in the range 1 ≦ q ≦ 10) _{, -C (CH 3) 2 -} , - C (CF 3) 2 -, and - (= O) functional group selected from NH-, especially, -S (= _{O) 2} - including those linked by, C6 to C30 groups, for example, aryl groups C6 to C30 or arylene of C6 to C30, Group, specifically, a C6-C16 aryl group or a C6-C16 arylene group such as a phenylene group, and "heterocyclic group" means O, S, N, P, Si and C2-C30 cycloalkyl group, C2-C30 cycloalkylene group, C2-C30 cycloalkenyl group, C2-C30 containing 1 to 3 heteroatoms selected from the group consisting of these combinations in one ring A C30 cycloalkenylene group, a C2-C30 cycloalkynyl group, a C2-C30 cycloalkynylene group, a C2-C30 heteroaryl group, or a C2-C30 heterocycle A lower arylene group, specifically, a C2-C15 cyclohexane containing 1 to 3 heteroatoms selected from the group consisting of O, S, N, P, Si and combinations thereof in one ring. Alkyl group, C2-C15 cycloalkylene group, C2-C15 cycloalkenyl group, C2-C15 cycloalkenylene group, C2-C15 cycloalkynyl group, C2-C15 cycloalkynylene group, C2-C15 heteroaryl Group or a C2-C15 heteroarylene group.

  In this specification, unless otherwise specified, “combination” means mixing or copolymerization.

  Furthermore, in this specification, “*” means a moiety linked to another atom.

One embodiment of the present invention includes a first imide repeating unit represented by the following general formula 3, an amic acid repeating unit that forms the imide repeating unit of the above general formula 3 by imidization, or a combination of these repeating units. A second repeating unit containing a repeating unit, an imide repeating unit represented by the following general formula 4, an amic acid repeating unit that forms an imide repeating unit represented by the above general formula 4 by imidization, or a combination of these repeating units A repeating unit represented by the following general formula 1, a repeating unit represented by the following general formula 2, or a third repeating unit containing a combination of these repeating units. And at least one end of the copolymer is substituted or unsubstituted siloxane. A copolymer others substituted by silanol groups,
Inorganic particles or precursors thereof;
A composite composition of copolymer and inorganic particles comprising:

In the above general formula 3 or general formula 4,
R ¹⁰ is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C1-C30 aliphatic organic group, a substituted or unsubstituted C3-C30 alicyclic organic group, substituted or non-substituted. A substituted C6-C30 aromatic organic group, or a substituted or unsubstituted C2-C30 heterocyclic group, specifically, a substituted or unsubstituted C1-C10 aliphatic organic group. , more specifically, -C _{(CF 3) 2} - may be.

R ¹¹ is the same or different in each repeating unit, and each independently includes a substituted or unsubstituted C 6 -C 30 aromatic organic group, and the aromatic organic group is a single aromatic ring, or 2 The above aromatic rings are bonded to each other to form a condensed ring, or two or more aromatic rings are a single bond, or a fluorenylene group, —O—, —S—, —C (═O) —, — _{CH (OH) -, - S} (= O) 2 -, - Si (CH 3) 2 -, - (CH 2) p - ( wherein, 1 ≦ p ≦ 10), - (CF 2) q - ( Here, it is connected by a functional group of 1 ≦ q ≦ 10), —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or —C (═O) NH—, specifically, At least one hydrogen atom of the aromatic organic group may be substituted with an electron withdrawing group. In this case, the electron-withdrawing _{group, -CF 3, -CCl 3, -CBr} 3, -CI 3, -F, -Cl, -Br, -I, -NO 2, -CN, -COCH 3 or -CO _Although it may be ₂ C ₂ H ₅ , it is not limited to this.

R ¹² and R ¹³ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, an ether group (—OR ²⁰⁸ , where R ²⁰⁸ is a C1-C10 aliphatic organic group), A silyl group (—SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substituted or An unsubstituted C1-C10 aliphatic organic group or a C6-C20 aromatic organic group.

  n7 and n8 are each independently an integer of 0 to 3.

In the above general formula 1,
R ¹ is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C3-C30 alicyclic organic group, a substituted or unsubstituted C6-C30 aromatic organic group, or substituted or unsubstituted An unsubstituted C2-C30 heterocyclic group, or a substituted or unsubstituted C13-C20 fluorenylene group.

R ² is the same or different in each repeating unit, and is independently a substituted or unsubstituted C6-C30 aromatic organic group, and may be specifically a phenylene group or a biphenylene group.

R ³ and R ⁴ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, or an ether group (—OR ²⁰⁰ , where R ²⁰⁰ is a C1-C10 aliphatic organic group). , A silyl group (—SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substitution Or it is an unsubstituted C1-C10 aliphatic organic group, or a C6-C20 aromatic organic group, and specifically, a hydrogen atom may be sufficient.

  n1 and n2 are each independently an integer of 0 to 4.

Specifically, R ¹ may be the same or different in each repeating unit, and may be independently selected from the group represented by the following general formula, but is not limited thereto.

Specifically, R ² may be the same or different in each repeating unit, and may be independently selected from the group represented by the following general formula, but is not limited thereto.

In the above general formula:
R ^{18 to} R ²⁹ are the same or different and each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted C1-C10 aliphatic organic group, or a substituted or unsubstituted C6-C20. An aromatic organic group,
n11 and n14 to n20 are each independently an integer of 0 to 4,
n12 and n13 are each independently an integer of 0 to 3.

More specifically, the R ² may be the same or different and may be independently selected from the group represented by the following general formula, but is not limited thereto.

In the above general formula 2,
R ⁵ is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C6-C30 aromatic organic group, and specifically, may be a phenylene group or a biphenylene group.

R ⁶ and R ⁷ are the same or different and are each independently an electron withdrawing group.

R ⁸ and R ⁹ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, or an ether group (—OR ²⁰⁴ , where R ²⁰⁴ is a C1-C10 aliphatic organic group). , A silyl group (—SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substitution Alternatively, it is an unsubstituted C1-C10 aliphatic organic group or a C6-C20 aromatic organic group.

n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3 + n5 is an integer of 4 or less,
n4 is an integer of 1 to 4, n6 is an integer of 0 to 3, and n4 + n6 is an integer of 4 or less.

Specifically, R ⁵ may be the same or different and may be independently selected from the group represented by the following general formula, but is not limited thereto.

In the above general formula:
The description of R ^{18 to} R ²⁹ and n11 to n20 is the same as the description for R ² .

Specifically, the ^{R 6} and ^{R 7} is an electron withdrawing group, the electron withdrawing _{group, -CF 3, -CCl 3, -CBr} 3, -CI 3, -F, -Cl, -Br, _-I, -NO _{2, -CN,} or it is also a -COCH ₃ or _-CO 2 _C 2 _{H 5,} but is not limited thereto.

More specifically, R ⁵ may be the same or different and may be independently selected from the group represented by the following general formula.

  The repeating unit represented by the above general formula 1, the repeating unit represented by the above general formula 2, or a combination of these repeating units is an amide repeating unit, and when these repeating units are included, solubility in a solvent, processability, It has excellent flexibility and optical properties, and can reduce the coefficient of thermal expansion. Accordingly, the copolymer including the repeating unit can have excellent optical characteristics, for example, transparency, excellent workability and flexibility, and a low thermal expansion coefficient.

  The copolymer has 1 to 1,000 third repeating units including the same or different repeating units represented by the above general formula 1, the repeating units represented by the above general formula 2, or a combination of these repeating units. May be included. When the copolymer contains the repeating unit within the above range, the optical properties, processability and flexibility of the copolymer containing the repeating unit can be effectively improved. Specifically, the copolymer includes one third repeating unit including the same or different repeating unit represented by the above general formula 1, the repeating unit represented by the above general formula 2, or a combination of these repeating units. ~ 100, more specifically 1-20 may be included.

  On the other hand, the third repeating unit may further include a repeating unit represented by the following general formula 6.

In the above general formula 6,
R ¹⁴ is the same or different in each repeating unit, and each independently represents —O—, —S—, —C (═O) —, —CH (OH) —, —S (═O) ₂ —, —Si (CH ₃ ) ₂ —, — (CH ₂ ) _p — (where 1 ≦ p ≦ 10), — (CF ₂ ) _q — (where 1 ≦ q ≦ 10), —C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -C (= O) NH-, or a substituted or unsubstituted C6-C30 aromatic organic group, wherein the aromatic organic group is a single aromatic ring Or two or more aromatic rings are bonded to each other to form a condensed ring, or two or more aromatic rings are a single bond, or a fluorenylene group, -O-, -S-, -C (= O _{) -, - CH (OH)} -, - S (= O) 2 -, - Si (CH 3) 2 -, - (CH 2) p - ( wherein, 1 ≦ p ≦ 1 _{), - (CF 2) q} - ( _{wherein, 1 ≦ q ≦ 10),} - C (CH 3) 2 -, - or by -C (= O) NH- functional group - C _{(CF 3) 2} Specifically, they may be linked by —S (═O) ₂ —.

R ¹⁵ is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C6-C30 aromatic organic group, and specifically, may be a phenylene group or a biphenylene group.

R ¹⁶ and R ¹⁷ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, or an ether group (—OR ²¹² , where R ²¹² is a C1-C10 aliphatic organic group). A silyl group (—SiR ²¹³ R ²¹⁴ R ²¹⁵ , wherein R ²¹³ , R ²¹⁴ and R ²¹⁵ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substitution Alternatively, it is an unsubstituted C1-C10 aliphatic organic group or a C6-C20 aromatic organic group.

  n9 and n10 are each independently an integer of 0 to 4.

  When the copolymer further includes a repeating unit represented by the general formula 6, the translucency of the copolymer can be improved.

  The imide repeating unit represented by the above general formula 3 or 4 or the amic acid repeating unit that forms the imide repeating unit represented by the above general formula 3 or 4 by imidation is excellent in heat resistance and mechanical strength. It is excellent in solvent resistance during the production of a molded product, and can suppress the formation of crystals during stretching. Accordingly, the copolymer including the first repeating unit and / or the second repeating unit can have excellent thermal characteristics and mechanical strength.

  The copolymer includes a imide repeating unit represented by the above general formula 3 that is the same or different from each other, an amic acid repeating unit that forms an imide repeating unit of the above general formula 3 by imidization, or a combination of these repeating units. 1 to 1,000 repeating units may be included. Specifically, it may contain 1 to 100 first repeating units, more specifically 1 to 20 first repeating units.

  The copolymer includes a second imide repeating unit represented by the above general formula 4 that is the same or different from each other, an amic acid repeating unit that forms an imide repeating unit of the above general formula 4 by imidization, or a combination of these repeating units. 1 to 1,000 repeating units may be included. Specifically, 1 to 100, more specifically 1 to 20 second repeating units may be included.

  When the repeating unit is included as the range, the thermal properties and mechanical strength of the copolymer can be effectively improved, and the optical properties can also be improved. Specifically, the imide repeating unit represented by general formula 3 or general formula 4 which is the same or different from each other, or the amide acid repeating unit which forms the imide repeating unit of general formula 3 or the imide repeating unit of general formula 4 by imidization. The unit may be 1 to 100, more specifically 1 to 20 units.

  The copolymer can have a weight average molecular weight of about 500 g / mol to about 200,000 g / mol. When the weight average molecular weight of the copolymer is within the above range, the thermal properties and mechanical strength of the copolymer can be effectively improved, and the optical properties can also be improved. Specifically, the copolymer can have a weight average molecular weight of about 5,000 g / mol to about 100,000 g / mol.

  On the other hand, the repeating unit represented by the general formula 3 includes an imide repeating unit represented by the following general formula 5 or an amic acid repeating unit capable of forming an imide repeating unit represented by the general formula 5 by imidization. Also good:

In the above general formula 5,
The description of R ¹¹ , R ¹² , R ¹³ , n7 and n8 is the same as the description in the general formula 3.

  When the repeating unit of the above general formula 3 includes the repeating unit represented by the above general formula 5, in the copolymer, the repeating unit represented by the above general formula 3 and / or the general formula 5 and / or the above general formula is represented by imidization. 3 and / or the total number of moles of the amic acid repeating unit forming the repeating unit of the general formula 5, the repeating unit represented by the general formula 4 and / or the amide forming the repeating unit of the general formula 4 by imidization The total number of moles of acid repeat units can have a molar ratio of about 99: 1 to about 1:99. In this case, the copolymer may have excellent heat resistance, mechanical strength, and flexibility, and may have excellent optical properties, specifically, translucency.

  In the copolymer, all repeating units included in the first repeating unit and all repeating units included in the second repeating unit may have a molar ratio of about 99: 1 to about 1:99.

  The copolymer includes 1 to 1,000 repeating units represented by the above general formula 1, the repeating unit represented by the above general formula 2, and the repeating unit represented by the above general formula 6 which are the same or different from each other. Also good.

  The copolymer has a molar ratio of about 95: 5 to about 5:95, wherein all the repeating units contained in the first repeating unit and the second repeating unit and all the repeating units contained in the third repeating unit are from about 95: 5 to about 5:95. Ratio, specifically, a molar ratio of about 90:10 to about 10:90.

  When the number of all repeating units contained in the copolymer and the molar ratio of all repeating units are within the above ranges, the copolymer can have excellent optical properties, heat resistance, mechanical strength and flexibility. .

  The repeating unit represented by the general formula 1 may include a repeating unit represented by the following general formulas 7 to 9, and the repeating unit represented by the general formula 2 is a repeating unit represented by the following general formulas 10 to 12. The repeating unit represented by the above general formula 3 (or general formula 5) may include a repeating unit represented by the following general formula 13, or the repeating unit represented by the above general formula 4. May contain a repeating unit represented by the following general formula 14, and the repeating unit represented by the above general formula 6 may contain a repeating unit represented by the following general formulas 15 to 17, It is not limited.

  In the composite composition of the copolymer and inorganic particles according to the embodiment, at least one terminal of the copolymer is substituted with a substituted or unsubstituted siloxane or silanol group.

  The substituted or unsubstituted siloxane or silanol group substituted on at least one terminal of the copolymer is a siloxane or silanol group represented by the following general formula 20:

In the general formula 20,
Ra is a substituted or unsubstituted alkyl group (alkylene group), a substituted or unsubstituted alkenyl group (alkenylene group), a substituted or unsubstituted alkynyl group (alkynylene group), a substituted or unsubstituted cycloalkyl group (cycloalkylene). Group), substituted or unsubstituted cycloalkenyl group (cycloalkenylene group), substituted or unsubstituted cycloalkynyl group (cycloalkynylene group), substituted or unsubstituted aryl group (arylene group), or substituted or unsubstituted It may be an aralkyl group (aralkylene group),
Rb to Rd are the same or different and are each independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, or a C6-C It may be a C18 aryl group.

  Specifically, the general formula 20 may be selected from the group represented by the following general formula, and is not limited thereto.

  In the above general formula, Re to Rg are the same or different and are each independently a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C3 to C20 cycloalkyl group, or a C6. It may be a C18 aryl group.

  When the siloxane or silanol group is substituted on one end of the copolymer to form a composition by mixing the copolymer and a precursor of inorganic particles or inorganic particles as described later, the inorganic particles or inorganic particles The precursors of the particles are evenly dispersed and well mixed with the copolymer without agglomerating within the composition by bonding to the siloxane or silanol ends of the copolymer, whereby the copolymer and the inorganic or inorganic particles The composition containing this precursor will exhibit high heat resistance and excellent optical properties.

  The siloxane or silanol group substituted at one terminal of the copolymer is subsequently crosslinked by hydrolysis with the inorganic particles or the precursor of the inorganic particles in the process of drying and heating the composition to produce a molded product. As a result, when the copolymer is formed into a film or the like, a cross-linking bond is formed between the copolymers, thereby realizing higher mechanical strength, heat resistance, and optical properties. it can. As described above, in the composition of the present invention, the siloxane or silanol group at the terminal of the copolymer and the inorganic particles are present in a state of helping the uniform dispersion of the inorganic particles by bonding by hydrogen bonding or the like at the time of mixing. Therefore, it cannot necessarily be said that it is an integrated form. However, when this composition is dried and heated to be molded, a cross-linking bond between the siloxane or silanol group at the terminal of the copolymer and the inorganic particles occurs to form an integral form.

  The inorganic particles or precursors thereof contained in the composite composition of the copolymer and inorganic particles are oxides or water of one or more elements selected from the group consisting of Ti, Si, Al, Zr, Sn, B, and Ce. An oxide or a precursor capable of forming the oxide or hydroxide is included.

  Specifically, the precursor compound capable of forming an oxide or hydroxide of the Ti, Si, Al, Zr, Sn, B, or Ce element is an alkoxide, ester, acetylacetonate, or halide (of the element). (halide; halide) may be used, but is not limited thereto.

Specifically, the inorganic particles are silica (SiO ₂ ) or TiO ₂ .

  The silica precursor may contain an organic silica precursor or an inorganic silica precursor, and the organic silica precursor may be a compound represented by the following general formula, but is not limited thereto:

In the above general formula:
Rh to Rm are the same or different and are each independently a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, or a C6-C18 aryl group. It may be.

  The inorganic silica precursor may include, but is not limited to, tetraethylorthosilicate (tetraethoxysilane; TEOS).

As a precursor of TiO ₂ , tetraisopropyl orthotitanate may be used, but is not limited thereto.

  The inorganic particles or inorganic particle precursors may be included in a content sufficient to provide from about 5 wt% to about 95 wt% inorganic particles based on the weight of the copolymer. Specifically, the inorganic particles or inorganic particle precursor is about 10 wt% to about 90 wt% based on the weight of the copolymer, more specifically about 15 wt% based on the weight of the copolymer. % To about 80% by weight of inorganic particles may be included.

  When the content range includes the inorganic particles or inorganic particle precursors, excellent heat resistance and a low coefficient of thermal expansion (CTE) are maintained while maintaining high optical properties as compared with the case of using only a polyimide copolymer. Can be realized.

  When the copolymer includes the inorganic particles or inorganic particle precursor, the composite composition including the copolymer and the inorganic particles or inorganic particle precursor has high mechanical strength, heat resistance, and excellent optical properties. Realized, the coefficient of thermal expansion (CTE) can be lowered, and the workability is further improved.

  Plastic substrates for displays are required to have high light transmittance, solvent resistance, low coefficient of thermal expansion (CTE), heat resistance, and the like. In particular, in the case of plastic substrates for organic light emitting diodes (OLED), oxide thin film transistors ( Oxide TFTs) or polysilicon thin film transistors (polysilicon TFTs) are exposed to (exposed to) a high temperature of 400 ° C. or higher. Therefore, it is necessary to maintain high heat resistance and colorlessness and transparency at high temperatures.

  However, in the case of most polymers, when exposed to a temperature of 400 ° C. or higher (exposed), it is often difficult to use as a substrate for OLED due to yellowing. In the case of polyimide which is generally used frequently, in order to improve the optical characteristics, a bulky side chain group or a kink structure is often introduced, or a fluorin compound is often used. There is a problem that the coefficient (CTE) becomes high. In the case of a polymer in which an alicyclic compound is introduced, it is possible to achieve translucency and a low coefficient of thermal expansion (CTE), but the thermal stability is insufficient and the problem of discoloration due to oxidation at high temperature is serious. is there.

However, the composite composition including the copolymer and the inorganic particles or the precursor thereof according to the above embodiment is based on a polyimide or poly (imide-amide) copolymer having transparent and colorless characteristics, and silica or TiO _{2 is used} here. By forming a composite composition containing inorganic particles or precursors thereof, high heat resistance, mechanical strength, and a low coefficient of thermal expansion (CTE) due to the inorganic particles or inorganic particle precursors are realized. . In particular, the composition has higher mechanical strength, heat resistance, and excellent optical properties by forming a crosslink between the copolymer and the inorganic particles or the precursor of the inorganic particles immediately upon forming the film. Realized.

  Further, as described above, by replacing siloxane or silanol groups at the oligomer ends in order to eliminate the problem of phase separation due to high packing of inorganic substances, these siloxane or silanol ends are the precursors of the inorganic particles or inorganic particles. The body and the copolymer form a crosslink, which results in higher mechanical strength and higher heat resistance and superior optical properties.

  Specifically, the polyimide copolymer (polyamide copolymer or poly (amide-imide) copolymer) may have a total light transmittance of about 80% or more in a wavelength range of about 380 nm to about 750 nm, and a wavelength of about 400 nm. The light transmittance for light may be about 55% or more. When the light transmittance of the polyimide copolymer (polyamide copolymer or poly (amide-imide) copolymer) is within the above range, the polyimide copolymer (polyamide copolymer or poly (amide-imide) copolymer) has transparency. It can be used for the production of molded products used in various fields that are required, and can have excellent color reproducibility. Specifically, the polyimide copolymer (polyamide copolymer or poly (amide-imide) copolymer) may have a total light transmittance of about 80% to about 95% in a wavelength range of about 380 nm to about 750 nm, The light transmittance for light having a wavelength of 400 nm may be about 55% to about 90%.

  On the other hand, the polyimide or poly (imide-amide) copolymer in the composition may be in any form such as a block copolymer, a random copolymer, and an alternating copolymer.

  Hereinafter, the manufacturing method of the composite composition containing the said copolymer and the said inorganic particle or its precursor is demonstrated.

  According to an embodiment of the present invention, a method for producing a copolymer including the first repeating unit and / or the second repeating unit and the third repeating unit may be obtained by using the above general formula 1 from a diamine and a dicarboxylic acid derivative. And a step of producing a monomer that is a repeating unit represented by the above general formula 2, or a combination of these repeating units, and an imide repeating unit represented by the above general formula 3 in the produced monomer, Alternatively, a monomer for producing an amic acid repeating unit that forms an imide of the above general formula 3 by imidization, and / or an imide repeating unit represented by the above general formula 4, or an imide of the above general formula 4 by imidization Add monomers to produce amic acid repeating units and copolymerize together Comprising a step, replacing said substituted or unsubstituted siloxane or silanol group at at least one end of the co-polymerized copolymer, a. In one embodiment, the copolymer may be independently substituted with the substituted or unsubstituted siloxane or silanol groups at both ends.

  The copolymers according to embodiments of the present invention can not be produced only in part by a specific method, but various related to the production of poly (imide-amide) copolymers known to those having ordinary knowledge in the art. It will be appreciated that the method can be used to manufacture.

  The repeating units of the above general formula 1 and general formula 2 are amide repeating units, and these are generally produced using, for example, a low temperature solution polymerization method, an interfacial polymerization method, a melt polymerization method, a solid phase polymerization method, and the like. However, it is not limited to this.

  Among these, a method for producing the amide repeating unit will be described by taking a low temperature solution polymerization method as an example. In the low temperature solution polymerization method, amide repeating units are produced by polymerizing carboxylic acid dichloride and diamine in an aprotic polar solvent.

  Examples of the aprotic polar solvent include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, and N, N. -Acetamide solvents such as diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol, etc. Phenolic solvents, hexamethylphosphoramide, γ-butyrolactone, and the like, which can be used alone or in combination. However, the present invention is not limited to this, and aromatic hydrocarbons such as xylene and toluene can also be used. In order to promote dissolution of the polymer, an alkali metal salt or an alkaline earth metal salt of about 50% by weight or less based on the total amount of the solvent can be further added to the solvent.

  In the presence of the aprotic polar solvent, for example, 4,4 ′-(9-fluorenylidene) dianiline (4,4 ′-(9-fluorenylidene) dianiline; BAPF ), 2,2′-bis (trifluoromethyl) benzidine (2,2′-bis (trifluoromethyl) benzidine; TFDB), 4,4′-diaminodiphenyl sulfone (DADPS), bis (4- (4-aminophenoxy) phenyl) sulfone (bis (4- (4-aminophenoxy) phenyl) sulfone; BAPS), 2,2 ′, 5,5′-tetrachlorobenzidine (2,2 ′, 5, 5'-tetrac lorobenzidine), 2,7-diaminofluorene, 1,1-bis (4-aminophenyl) cyclohexane (1,1-bis (4-aminophenyl) cyclohexane), 4,4′-methylenebis- (2-methylcyclohexylamine) (4,4′-methylenebis- (2-methylcyclohexylamine)), 4,4-diaminooctafluorobiphenyl, 3,3′-dihydroxybenzidine (3,3 ′ -Dihydroxybenzidine), 1,3-cyclohexanediamine (1,3-cyclohexanediamine) and combinations thereof Diamines selected from the group such as, for example, terephthaloyl chloride (TPCl), isophthaloyl chloride (IPCl), biphenyl dicarbonyl chloride (BPCl), naphthalene diphenyl chloride It can be obtained by mixing and reacting with a carboxylic acid dichloride selected from the group consisting of dicarbonyl chloride, 2-fluoro-trephthaloyl chloride and combinations thereof. At this time, it goes without saying that the types and amounts of the diamine and the carboxylic acid dichloride can be appropriately selected and used in accordance with the desired composition of the repeating unit of the general formula 1 or the repeating unit of the general formula 2. Nor.

  On the other hand, when the diamine is used in excess of the carboxylic acid dichloride in the production of the repeating unit of the general formula 1 or the repeating unit of the general formula 2, an amine group is present at the terminal of the produced repeating unit. May be.

  On the other hand, the repeating units of the above general formula 3 and general formula 4 are imide repeating units, and these imides (polyimides) are generally amide acids (polyamide acids; polyamic acids) that are precursors of imides (polyimides). After the production, it can be produced by a usual method of imidizing it. For example, amide acid (polyamide acid; polyamic acid), which is a precursor of imide (polyimide), can be produced by reacting tetracarboxylic dianhydride with diamine, and this can be produced by thermal or chemical imidization. Polyimide can be produced.

  As an example, for the production of the amic acid (polyamic acid; polyamic acid), for example, 2,2-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis- ( 3,4-dicarboxylicboxyl) hexafluoropropane dianhydride; 6FDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride), PD Hydride (benzophenone tetracarboxylic dianhydride; BTDA), bis (3,4-dicarboxyphenyl) sulfo A tetracarboxylic dianhydride selected from the group consisting of bis (3,4-dicboxyphenyl) sulfone dianhydride and combinations thereof, for example, 2,2′-bis (trifluoromethyl) benzidine (2,2 '-Bis (trifluoromethyl) benzidine; TFDB), 4,4'-diaminodiphenyl sulfone (DADPS), 4,4'-(9-fluorenylidene) dianiline (4,4 '-(9 -Fluorenylidene) dianline; BAPF), bis (4- (4-aminophenoxy) phenyl) sulfone (bis (4- (4-aminophenoxy) phenyl) s BAPS), 2,2 ′, 5,5′-tetrachlorobenzidine (2,2 ′, 5,5′-tetrachlorobenzidine), 2,7-diaminofluorene, 1,1- Bis (4-aminophenyl) cyclohexane (1,1-bis (4-aminophenyl) cyclohexane), 4,4′-methylenebis- (2-methylcyclohexylamine) (4,4′-methylenebis- (2-methylcyclohexylamine)) 4,4-diaminooctafluorobiphenyl, 3,3′-dihydroxybenzidine, 1,3, 4,4-diaminooctafluorobiphenyl, 3,3′-dihydroxybenzidine, 1,3 -It can manufacture using the diamine chosen from the group which consists of cyclohexanediamine (1,3-cyclohexaneamine) and these combination. At this time, it goes without saying that the types and amounts of the tetracarboxylic dianhydride and the diamine can be appropriately selected and used according to the desired composition.

  On the other hand, when the diamine is used in excess of the tetracarboxylic dianhydride in the production of the amic acid (polyamic acid; polyamic acid), an amine group may be present at the terminal of the produced copolymer. .

  In the above, the production method of the polyamide containing the repeating unit of the general formula 1 and / or the general formula 2 and the production method of the polyimide containing the repeating unit of the general formula 3 and / or the general formula 4 are respectively described. When producing a poly (amide-imide) copolymer according to an embodiment, the monomers forming the respective repeating units are mixed together and polymerized, or after the monomer containing the amide repeating unit is first produced. A poly (amide-imide) copolymer can also be produced by adding a monomer for imide production and copolymerizing it.

  A siloxane or silanol group is substituted at one end of the copolymer prepared as described above. That is, by adding the above-mentioned compound containing a siloxane or silanol group of the general formula 20 to the prepared poly (amide-imide) copolymer solution, and stirring and mixing it, (at least) one end of the copolymer A poly (amide-imide) copolymer substituted with a siloxane or silanol group is obtained.

  Thus, the substitution of the siloxane or silanol group at (at least) one end of the copolymer is performed simply by mixing the compound containing the siloxane or silanol group into the solution containing the copolymer after the production of the copolymer.

  Hereinafter, a method for producing a composite composition containing the produced copolymer having at least one siloxane or silanol group substituted at one end and inorganic particles or inorganic particle precursors will be described. The manufacturing method of this composite composition is also simple.

  That is, a solution containing inorganic particles or a precursor of inorganic particles is added to the produced copolymer having at least one siloxane or silanol group substituted at one end, and these are mixed and stirred to obtain the siloxane. Alternatively, a composite composition comprising a copolymer substituted with silanol groups and inorganic particles or a precursor thereof can be produced.

  The composite composition can be formed into an organic polymer film containing inorganic nanoparticles by coating it on a substrate and drying it.

  The copolymer according to the embodiment can be produced as an oligomer or a high molecular weight polymer by appropriately adjusting the molecular weight according to a desired application.

  When manufactured as an oligomer, it has a low viscosity and is suitable for spin coating used in the manufacture of substrates for OLEDs. That is, a transparent substrate film for OLED can be easily produced immediately by spin-coating the composite composition of oligomer and inorganic particles produced as described above on a substrate and drying it. . Although it is not easy to produce an optical film using an oligomer, when using a composite composition of an oligomer and inorganic particles according to an embodiment of the present invention, as described above, (at least) of the oligomer Sufficient tensile strength, mechanical strength, and high heat resistance are achieved by forming a siloxane or silanol group substituted at one end and the inorganic particle or inorganic particle precursor forms a cross-link bond in situ at the same time as the film is formed. And an optical film that maintains a low coefficient of thermal expansion (CTE) and transparency.

  Therefore, in still another embodiment of the present invention, a molded article including a composite of the copolymer and inorganic particles is provided.

  The molded product may be a film, a fiber, a coating material, an adhesive, or the like, but is not limited thereto.

  The molded product may be formed by a dry / wet method, a dry method, a wet method, or the like using a composite composition of the copolymer and inorganic particles, but is not limited thereto. Specifically, as described above, the molded article may be an optical film. In this case, the composite composition of the copolymer and the inorganic particles is applied onto a substrate by a method such as spin coating. After that, it can be easily manufactured by drying and curing.

  The molded article containing the composite of the copolymer and the inorganic particles may have a total light transmittance of about 70% or more, specifically (preferably) about 75% or more in a wavelength range of 360 nm to 700 nm. The light transmittance for light having a wavelength of 430 nm may be about 55%, specifically (preferably) about 60% or more. When the light transmittance of the molded product containing the composite of the copolymer and inorganic particles is within the above range, the molded product can have excellent color reproducibility. Specifically (preferably), the molded article may have a total light transmittance of about 75% to about 95% in a wavelength range of 360 nm to 750 nm, and a light transmittance of about 430 nm light. It may be 60% to about 90%.

  The molded article may have a coefficient of thermal expansion (CTE) of about 30 ppm / ° C. or less. When the thermal expansion coefficient of the molded product is within the above range, it can have excellent heat resistance. Specifically, the molded article may have a thermal expansion coefficient of about 25 ppm / ° C. or less, more specifically about 20 ppm / ° C. or less.

  The molded article has a glass transition temperature (Tg) of about 400 ° C. or higher. The composite composition of a copolymer and inorganic particles according to an embodiment of the present invention can significantly improve the glass transition temperature to 400 ° C. or more by introducing the inorganic particles, and such a high glass transition temperature is It is very important for high temperature processes such as OLED manufacturing.

  The molded article may have a haze of about 7% or less. When the haze range of the molded product is within the above range, the molded product is sufficiently transparent, and thus can have excellent sharpness. Specifically, the molded article may have a haze of about 5% or less, more specifically about 3% or less.

  The molded article may have a yellow index (YI) of about 20% or less. When the yellowness of the molded product is within the above range, it may be transparent and colorless.

  When the molded article is a film, for example, it may have a thickness of about 0.01 μm to about 1,000 μm, but is not limited thereto, and the thickness is appropriately adjusted according to the application. be able to.

  The molded article has the transparency, heat resistance, mechanical strength, and low coefficient of thermal expansion (CTE) as described above, and maintains the flexibility of the copolymer as it is. Substrate, display substrate, optical film, integrated circuit (IC) package, electrodeposited film, multi-layer flexible printed circuit (FRC), tape, touch panel, optical disk protection It can be used in various fields such as film.

  According to still another embodiment of the present invention, a display device including the molded product is provided. Specifically, the display device may be a liquid crystal display device (LCD), an organic light emitting diode, or the like, but is not limited thereto.

  A liquid crystal display device (LCD) among the display devices will be described with reference to FIG. FIG. 1 is a cross-sectional view of a liquid crystal display device according to an embodiment of the present invention.

  Referring to FIG. 1, the liquid crystal display device includes a thin film transistor display panel 100, a common electrode display panel 200 facing the thin film transistor display panel 100, and a liquid crystal layer 3 sandwiched between the display panels 100 and 200.

  First, the thin film transistor array panel 100 will be described.

  On the substrate 110, a gate electrode 124, a gate insulating film 140, a semiconductor 154, a plurality of resistive contact members 163 and 165, a source electrode 173, and a drain electrode 175 are formed in this order. The source electrode 173 and the drain electrode 175 are separated from each other and face each other with the gate electrode 124 as the center.

  One gate electrode 124, one source electrode 173, and one drain electrode 175 form one thin film transistor (TFT) together with the semiconductor 154, and the channel of the thin film transistor includes the source electrode 173 and the drain electrode 175. Is formed in the semiconductor 154 therebetween.

  A protective film 180 is formed on the gate insulating film 140, the source electrode 173, and the drain electrode 175, and a contact hole 185 that exposes the drain electrode 175 is formed in the protective film 180.

  A pixel electrode 191 made of a transparent conductive material such as ITO or IZO is formed on the protective film 180. The pixel electrode 191 is connected to the drain electrode 175 through the contact port 185.

  Next, the common electrode panel 200 will be described.

  In the common electrode panel 200, a light shielding member 220 called a black matrix is formed on a substrate 210, and a color filter 230 is formed on the substrate 210 and the light shielding member 220. A common electrode 270 is formed.

  At this time, the substrates 110 and 210 may be manufactured from a molded product including a composite of the poly (amide-imide) copolymer and inorganic particles.

  Meanwhile, an organic light emitting diode (OLED) in the display device will be described with reference to FIG. FIG. 2 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.

  Referring to FIG. 2, the thin film transistor 320, the capacitor 330, and the organic light emitting device 340 are formed on the substrate 300. The thin film transistor 320 includes a source electrode 321, a semiconductor layer 323, a gate electrode 325 and a drain electrode 322, the capacitor 330 includes a first capacitor 331 and a second capacitor 332, and the organic light emitting device 340 includes a pixel. An electrode 341, an intermediate layer 342, and a counter electrode 343 are provided.

  Specifically, the semiconductor layer 323, the gate insulating film 311, the first capacitor 331, the gate electrode 325, the interlayer insulating film 313, the second capacitor 332, and the source electrode 321 are formed on the substrate 300. In addition, a drain electrode 322 is formed. The source electrode 321 and the drain electrode 322 are separated from each other and face each other with the gate electrode 325 as the center.

  A planarization film 317 is formed on the interlayer insulating film 313, the second capacitor 332, the source electrode 321, and the drain electrode 322, and a contact hole 319 exposing the drain electrode 322 is formed in the planarization film 317. Is formed.

  A pixel electrode 341 made of a transparent conductive material such as ITO or IZO is formed on the planarizing film 317. The pixel electrode 341 is connected to the drain electrode 322 through the contact port 319.

  On the pixel electrode 341, an intermediate layer 342 and a counter electrode 343 are formed in this order.

  A pixel limiting film 318 is formed on the planarizing film 317 at a location where the pixel electrode 341, the intermediate layer 342, and the counter electrode 343 are not formed.

  At this time, the substrate 300 may be manufactured from a molded article including a composite of the poly (amide-imide) copolymer and inorganic particles.

  Hereinafter, embodiments of the present invention will be described with reference to examples. These examples are for explaining embodiments of the present invention, and do not limit the scope of the present invention.

Examples Synthesis Example 1: Synthesis of Oligo (Amido-Amic Acid) Substituted with Siloxane Group According to the following reaction formula 1, DA119 containing the repeating unit of the above general formula 2 was produced.

  That is, the DA119 monomer corresponding to the amide repeating unit is added to 2,2′-bis (trifluoromethyl) in 800 g of N, N-dimethylacetamide (DMCA; N, N-dimethylacetamide) as a solvent in a round bottom flask. ) After dissolving 2 molar equivalents (0.08 mol, 25.6192 g) of benzidine (2,2′-bis (trifluoromethyl) benzidine; TFDB) and 2.2 molar equivalents of pyridine (0.088 mol, 6.96 g). The remaining TFDB was washed with 80 ml of DMAC. Biphenyldicarbonyl chloride (BPCl) 11.648 g (1 molar equivalent, 0.04 mol) was mixed in 4 portions with the TFDB solution at 5 ° C. and stirred vigorously for 15 minutes.

  The resulting solution (resulting solution) was stirred in a nitrogen atmosphere for 2 hours, and then cooled to 0 ° C. in 7 L of water containing 1 kg of NaCl. The resulting mixture (resulting mixture) was cooled to 0 ° C. over 12 hours to complete the organic precipitation. The solid was filtered, resuspended and refiltered 4 times in 1.5 L of deionized water. The final filtrate on the filter was appropriately pressurized to remove the remaining water to the maximum and dried with a stream of nitrogen until it had a predetermined weight. The pre-dried product is further kept for 36 hours in a vacuum desiccator containing sodium hydroxide and nitrogen atmosphere to remove the residue and dried under vacuum at 90 ° C. to obtain the product described in Reaction Scheme 1. DA119 which is a monomer was obtained.

  In a 250 ml 4-neck double walled reactor equipped with a mechanical stirrer and nitrogen inlet, 4.4119 g (0.0052 mol) of the prepared DA119 and 2.2226 g of TFDB (0.25 g) were added. 0069 mol) was added to 39.97 g of NMP (N-methyl-2-pyrrolidone) at 80 ° C. and stirred until it was completely dissolved. After the temperature was lowered to 20 ° C., 0.5994 g (0.0013 mol) of 6-FDA (4,4′-hexafluoroisopropylidene) diphthalic anhydride), BPDA (3,3′-4,4′-biphenyl) Tetracarboxylic dianhydride) 3.5729 g (0.0121 mol) and NMP 9.234 g were gradually added and reacted for 24 hours to give a solid content of 15 wt% solid hydride-terminated oligo (amide-amide acid). ) 3-Aminopropyltriethoxysilane (APS) was gradually added to this solution, and then reacted over 6 hours to react with oligo (amide-amide acid (PAD) substituted with a siloxane group. -573) A solution was obtained (see FIG. 3).

Synthesis Example 2: Production of oligo (amide-amide acid) silica nanocomposite substituted with a siloxane group and production of a film using this nanocomposite production process is simply shown in FIG.

Specifically, 5 g (18 wt% solid content) of oligo (amide-amido acid) PAD-573 (solution) terminal-substituted with the siloxane group produced in Synthesis Example 1 was placed in a 20 ml vial. . Next, 0.3086 g of tetraethyl orthosilicate (tetraethoxysilane; TEOS) (manufactured by Samchun Pure Chemical Co., 99%) and 0.1308 g of H ₂ O / NMP (4: 6 (mass ratio) mixture) were added. Placed in the vial. The mixture was stirred for 24 hours and spin cast on a glass substrate.

  In order to obtain a high silica content, 50% by weight and 60% by weight of tetramethylorthosilicate (TMOS) (manufactured by Aldrich, 99%) relative to the solid content of the PAD-573 was used in the same manner as described above. A mixture was obtained and the mixture was stirred for 24 hours and spin cast on a glass substrate.

  Specifically, the mixture was instilled onto a glass substrate (5 × 5 cm) and spin-coated at a rotation speed of 800 rpm. The spin-coated solution was pre-dried on a hot plate at 80 ° C. for 1 hour to evaporate excess solvent. The glass substrate was heated to 320 ° C. at a rate of 3 ° C./min in a nitrogen atmosphere, and then cured at 320 ° C. for 1 hour.

  All manufactured films were placed in a furnace heated to 400 ° C. for 30 minutes for thermal stability testing.

The theoretical molar composition for the prepared polyimide-amide (PIA) film substituted at both ends with siloxane groups is shown in Table 1 below. PIA10 means that the theoretical content of SiO ₂ is 10% by weight, and PIA20 means that the theoretical content of SiO ₂ is 20% by weight. The rest should be interpreted in the same way as above.

Experimental example: film performance evaluation Experimental example 1: Translucency (transmittance)
The optical properties of the films produced using the transmission opaque / haze mode of a Konica Minolta CM 2600d spectrophotometer were measured. Spectra were recorded in the wavelength range of 360 nm to 700 nm.

Experimental Example 2: Thermal expansion coefficient (CTE) and glass transition temperature (Tg)
The thermal expansion coefficient (CTE) was measured by TMA Q400 (TA Instruments, USA) by the following heating program. As the measurement value, the second scan value was adopted, and the measurement temperature interval was 50 ° C. to 300 ° C .:
First scan condition: 5 minutes isothermal maintenance → Heat to 300 ° C at 5 ° C / min heating rate → Cool to 40 ° C Second scan condition: Heat to 400 ° C at 5 ° C / min heating rate .

  The optical characteristics of the film produced in Synthesis Example 2 are shown in FIGS. As is apparent from FIGS. 5 and 6, the light transmittance (transmittance) of the film increased as the silica content increased. However, it can be seen that when the silica content increases to 50% and 60% or more, the light transmittance (transmittance) decreases due to the aggregation of silica, and the haze also becomes 7% or more (see Table 2 below).

  FIG. 7 shows the translucency (transmittance) of the polymer film at 430 nm and the entire wavelength range (360 nm to 740 nm) after the film was heated at 400 ° C. for 30 minutes. The PIA nanocomposite film exhibits higher transmittance (transmittance) than a PIA film that is a pure polymer film. In particular, when the silica content was 40% and 50%, the translucency (transmittance) of the polymer film at 430 nm was 80.08% and 74.74%, respectively.

  Table 2 below summarizes the optical characteristics according to the silica content of the film.

Experimental Example 3: Thermogravimetric analysis (TGA)
The thermal stability of the nanocomposite was measured using a TGA Q500 thermogravimetric analyzer (TA Instruments, USA) at a heating rate of 10 ° C./min in a nitrogen atmosphere (gas flow rate: 70 ml / min). Then, measurement was performed on samples 10 to 15 mg in Al ₂ O ₃ heated from 25 ° C. to 600 ° C.

  FIG. 8 is a graph showing the dimensional change of the film according to the silica content.

  As is clear from FIG. 8, in the case of a pure PIA film (silica content; 0% graph in the figure), the change in size increases rapidly at 300 ° C. or higher, but the silica content (10% → As the temperature increases to 40% (both mass%)), the degree of dimensional change of the film is weakened even if the temperature is raised to a high temperature, for example, 400 ° C. (see the graph of 10% to 40% in the figure).

  Table 3 below collectively shows Td (thermal decomposition temperature), Tg (glass transition temperature), and thermal expansion coefficient (CTE) measured in the range of 50 ° C to 300 ° C.

  As apparent from Table 3 above, in the case of the composite film containing silica, the average coefficient of thermal expansion (CTE) value in the range of 50 ° C to 300 ° C is 14.44 to 28.20 ppm / ° C. The introduction of silica raises the glass transition temperature to 400 ° C. or more, which is a very important characteristic in the production process of an optical film such as an OLED. The increase in the Tg of the nanocomposite film is manifested when the organic polymer chain is cross-linked with the silica particles, indicating a stronger interaction between the organic polymer and the inorganic particles.

Experimental Example 4: Measurement of refractive index and evaluation of silica content The refractive index of the nanocomposite was measured at 633 nm using a prism coupler Metricon MODEL 2010 / M. The content of silica was calculated according to the Lorentz-Lorentz equation represented by the following formula (1).

Where n, n _s and n _p are measured relative to the refractive index of the composite, silica and pure polymer, and v _s and v _p denote the volume fraction of silica and pure polymer.

  As described above, the composite composition of the copolymer and the inorganic particles according to the embodiment of the present invention allows the introduction of the inorganic particles while maintaining the flexible characteristics of the copolymer (polyimide-amide; PIA) as it is. A substrate for a flexible OLED display device that requires a process at a high temperature of 400 ° C. or higher by having higher heat resistance, mechanical strength, and transparency, and having a lower coefficient of thermal expansion (CTE) It can be seen that it provides suitable characteristics when used as a material.

  The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to these embodiments, and various modifications may be made within the scope of the following claims, the detailed description of the invention, and the accompanying drawings. Needless to say, this is also within the scope of the present invention.

100: Thin film transistor display panel,
200: Common electrode display board,
110, 210, 300: substrate,
124: a gate electrode,
140: a gate insulating film,
154: Semiconductor,
163, 165: resistive contact members,
173: source electrode,
175: drain electrode,
180: protective film,
185: contact opening,
191: Pixel electrode,
220: a light shielding member,
230: Color filter,
270: Common electrode,
311: gate insulating film,
313: Interlayer insulating film,
317: planarization film,
318: Pixel limiting film,
319: contact port,
320: thin film transistor,
321: source electrode,
322: drain electrode,
323: Semiconductor layer
325: a gate electrode,
330: Capacitor,
331: first capacitor,
332: second capacitor,
340: organic light emitting device,
341: pixel electrode,
342: middle layer,
343: counter electrode.

Claims (15)

In the general formula 4, an imide repeating unit represented by the following general formula 3, an amic acid repeating unit that forms the imide repeating unit of the general formula 3 by imidization, or a combination of these repeating units; One or more of an imide repeating unit represented, an amic acid repeating unit that forms an imide repeating unit represented by the above general formula 4 by imidization, or a second repeating unit containing a combination of these repeating units; A copolymer comprising a repeating unit represented by the following general formula 1, a repeating unit represented by the following general formula 2, or a third repeating unit including a combination of these repeating units,
At least one end of the copolymer is substituted with a substituted or unsubstituted siloxane or silanol group;
Inorganic particles or precursors thereof;
A composite composition comprising:
(In the above general formula 3 or general formula 4,
R ¹⁰ is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C1-C30 aliphatic organic group, a substituted or unsubstituted C3-C30 alicyclic organic group, a substituted or unsubstituted A C6-C30 aromatic organic group, or a substituted or unsubstituted C2-C30 heterocyclic group,
R ¹¹ is the same or different in each repeating unit, and each independently includes a substituted or unsubstituted C6-C30 aromatic organic group, and the aromatic organic group is one aromatic ring, Two or more aromatic rings are bonded to each other to form a condensed ring, or two or more aromatic rings are a single bond, or a fluorenylene group, -O-, -S-, -C (= O)-,- _{CH (OH) -, - S} (= O) 2 -, - Si (CH 3) 2 -, - (CH 2) p - ( wherein, 1 ≦ p ≦ 10), - (CF 2) q - ( Here, 1 ≦ q ≦ 10), —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or —C (═O) NH— is connected by a functional group,
R ¹² and R ¹³ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, an ether group (—OR ²⁰⁸ , where R ²⁰⁸ is a C1-C10 aliphatic organic group). , A silyl group (—SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substitution Or an unsubstituted C1-C10 aliphatic organic group, or a C6-C20 aromatic organic group,
n7 and n8 are each independently an integer of 0 to 3. )
(In the above general formula 1,
R ¹ is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C3-C30 alicyclic organic group, a substituted or unsubstituted C6-C30 aromatic organic group, or a substituted or non-substituted group. Containing a substituted C2-C30 heterocyclic group,
R ² is the same or different in each repeating unit, and each independently represents a substituted or unsubstituted C6-C30 aromatic organic group;
R ³ and R ⁴ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, or an ether group (—OR ²⁰⁰ , where R ²⁰⁰ is a C1-C10 aliphatic organic group). , A silyl group (—SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substitution Or an unsubstituted C1-C10 aliphatic organic group, or a C6-C20 aromatic organic group,
n1 and n2 are each independently an integer of 0 to 4. )
(In the above general formula 2,
R ⁵ is the same or different in each repeating unit, each independently a substituted or unsubstituted C6-C30 aromatic organic group,
R ⁶ and R ⁷ are the same or different and are each independently an electron withdrawing group;
R ⁸ and R ⁹ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, an ether group (—OR ²⁰⁴ , where R ²⁰⁴ is a C1-C10 aliphatic organic group), A silyl group (—SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substituted or An unsubstituted C1-C10 aliphatic organic group, or a C6-C20 aromatic organic group,
n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3 + n5 is an integer of 4 or less,
n4 is an integer of 1 to 4, n6 is an integer of 0 to 3, and n4 + n6 is an integer of 4 or less. )   The composite composition according to claim 1, wherein the copolymer includes all of the first repeating unit, the second repeating unit, and the third repeating unit. The repeating unit represented by the above general formula 3 includes a repeating unit represented by the following general formula 5 or an amic acid repeating unit capable of forming a repeating unit represented by the above general formula 5 by imidization. The composite composition according to 2:
In the above general formula 5,
R ¹¹ , R ¹² , R ¹³ , n7 and n8 are the same as described in the section of claim 1. In the general formula 1, the R ¹ is selected from the group represented by the following general formula:
In the general formula 2, wherein ^{R 6} and ^{R 7} are the same or different and are _{independently, -CF 3, -CCl 3, -CBr} 3, -CI 3, -F, -Cl, -Br, -I , _-NO 2, -CN, a -COCH ₃ or _-CO 2 _C 2 _{H 5,}
In said general formula 1 and said general formula 2, said R < ² > and R < ⁵ > are the same or different, and are each independently selected from the group represented by the following general formula, Any one of Claims 1 thru | or 3 The composite composition according to claim 1:
In the above general formula:
R ^{18 to} R ²⁹ are the same or different and are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted C1-C10 aliphatic organic group, or a substituted or unsubstituted C6-C20 aromatic. Group organic group,
n11 and n14 to n20 are each independently an integer of 0 to 4,
n12 and n13 are each independently an integer of 0 to 3. The composite composition according to claim 4, wherein R ² and R ⁵ are the same or different and are each independently selected from the group represented by the following general formula:
The composite composition according to any one of claims 1 to 5, wherein the third repeating unit further includes a repeating unit represented by the following general formula 6.
In the above general formula 6,
R ¹⁴ is the same or different in each repeating unit, and each independently represents —O—, —S—, —C (═O) —, —CH (OH) —, —S (═O) ₂ —, —Si (CH ₃ ) ₂ —, — (CH ₂ ) _p — (where 1 ≦ p ≦ 10), — (CF ₂ ) _q — (where 1 ≦ q ≦ 10), —C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -C (= O) NH-, or a substituted or unsubstituted C6-C30 aromatic organic group, wherein the aromatic organic group is one aromatic Or two or more aromatic rings are bonded to each other to form a condensed ring, or two or more aromatic rings are a single bond, or a fluorenylene group, -O-, -S-, -C (= O) -, - CH (OH ) -, - S (= O) 2 -, - Si (CH 3) 2 -, - (CH 2) p - ( wherein, 1 ≦ p ≦ _{0), - (CF 2)} q - ( _{wherein, 1 ≦ q ≦ 10),} - C (CH 3) 2 -, - C (CF 3) 2 - or -C (= O) NH- functional groups Connected by
R ¹⁵ is the same or different in each repeating unit, each independently a substituted or unsubstituted C6-C30 aromatic organic group;
R ¹⁶ and R ¹⁷ are the same or different and are each independently a hydrogen atom, a halogen atom, a hydroxy group, or an ether group (—OR ²¹² , where R ²¹² is a C1-C10 aliphatic organic group). A silyl group (—SiR ²¹³ R ²¹⁴ R ²¹⁵ , wherein R ²¹³ , R ²¹⁴ and R ²¹⁵ are the same or different and are each independently a hydrogen atom or a C1-C10 aliphatic organic group), substitution Or an unsubstituted C1-C10 aliphatic organic group, or a C6-C20 aromatic organic group,
n9 and n10 are each independently an integer of 0 to 4. The repeating unit represented by the general formula 1 includes a repeating unit represented by the following general formulas 7 to 9,
The repeating unit represented by the general formula 2 includes a repeating unit represented by the following general formulas 10 to 12,
The repeating unit represented by the general formula 3 includes a repeating unit represented by the following general formula 13,
The repeating unit represented by the general formula 4 includes a repeating unit represented by the following general formula 14,
The complex composition according to claim 6, wherein the repeating unit represented by the general formula 6 includes a repeating unit represented by the following general formulas 15 to 17:
The copolymer is
A repeating unit represented by the following general formula 10;
A repeating unit represented by the following general formula 13;
A repeating unit represented by the following general formula 14;
The composite composition according to any one of claims 1 to 7, comprising:
The composite composition according to any one of claims 1 to 8, wherein the siloxane or silanol group is represented by the following general formula 20.
In the general formula 20,
Ra is a substituted or unsubstituted alkyl group or alkylene group, a substituted or unsubstituted alkenyl group or alkenylene group, a substituted or unsubstituted alkynyl group or alkynylene group, a substituted or unsubstituted cycloalkyl group or cycloalkylene group, substituted Or an unsubstituted cycloalkenyl group or cycloalkenylene group, a substituted or unsubstituted cycloalkynyl group or cycloalkynylene group, a substituted or unsubstituted aryl group or arylene group, or a substituted or unsubstituted aralkyl group or aralkylene group. ,
Rb to Rd are the same or different and are each independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, or a C6-C C18 aryl group. The composite composition according to claim 9, wherein the general formula 20 is selected from the group represented by the following general formula:
In the above general formula, Re to Rg are the same or different and are each independently a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C3 to C20 cycloalkyl group, or a C6. Is a C18 aryl group.   The inorganic particles contained in the composite composition or precursors thereof are oxides or hydroxides of one or more elements selected from the group consisting of Ti, Si, Al, Zr, Sn, B and Ce, or The composite composition according to any one of claims 1 to 10, which is a precursor capable of forming an oxide or a hydroxide. The composite composition according to any one of claims 1 to 11, wherein the inorganic particles are silica (SiO ₂ ) or TiO ₂ . The composite according to claim 12, comprising tetraisopropyl orthotitanate as the precursor of TiO ₂ , or comprising tetraethyl orthosilicate (TEOS) or a compound represented by the following general formula as the precursor of the silica. Composition:
In the above general formula:
Rh to Rm are the same or different and are each independently a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, or a C6-C18 aryl group. It is.   14. The inorganic particle or inorganic particle precursor is included in a content sufficient to provide from about 5 wt% to about 95 wt% inorganic particles, based on the weight of the copolymer. The composite composition according to any one of the above.   A molded article comprising the composite composition according to any one of claims 1 to 14.